Templates Regulate The Self-assembly Of Alkenyl Complexes And Their [2+2] Cycloaddition Reactions

Solid state[2+2]photocycloaddition reactions which occurred in photochemically active coordination polymers（CPs）have attracted intensive attention of chemists due to their potential applications in the synthesis of complicated organic compounds,the structural transformation of compounds and electrochemical properties and etc.In this thesis therefore different templates are used to effectively regulate the pre-arrangement of photoactive molecules in the self-assembly process of CPs,and the[2+2]photochemical reactivity of the obtained complexes were also investigated.The detailed results are described as followed:1.In order to investigate the influence of coordination bond templates on the self-assembly and the[2+2]cycloaddition reaction of CPs,we therefore selected three carboxylic acid ligands reacted with bpe and Zn or Cd salts,and three new CPs,namely,[Cd₃（bpe）₂（cba）₂（fa）₂（H₂O）₂]_n（1）,[Cd₂（bpe）₂（cpa）₂]_n（2）and{[Zn₂（bpe）（boaba）（μ₃-OH）]·3H₂O}_n（3）were prepared under hydrothermal conditions.All the CPs with single-crystal-to-single-crystal（SCSC）fashion under the UV irradiation converted into their corresponding photochemical dimerization products,namely,[Cd₃（rctt-tpcb）（cba）₂（fa）₂（H₂O）₂]_n（1a）,[Cd₂（rctt-tpcb）（cpa）₂]_n（2a）and{[Zn₄（rctt-tpcb）（boaba）₂（μ₃-OH）₂]·2H₂O}_n（3a）,respectively.2.Two photoreactive one-dimensional CPs{[Zn₂（Hoabdc）₂（bpeb）₂]?2H₂O}_n（4）and{[Zn（boaba）（Hbpeb）₂]?H₂O}_n（5）were obtained by the self-assembly of bpeb and H₃oabdc or H₃boaba in the presence of Zn（NO₃）₂·6H₂O under hydrothermal conditions.Upon exposure to UV irradiation,both CPs via SCSC fashion are transformed into their corresponding photodimerization products{[Zn₂（Hoabdc）₂（bpbpvpcb）]?H₂O}_n（4a）and{[Zn₂（boaba）₂（H₂bpbpvpcb）]?H₂O}_n（5a）,respectively.